Water-insoluble azo dyestuffs



Patented June 6, 1939 UNITED STATES PATENT OFFICE v WATER-INSOLUBLE AZO DYESTUFFS Josef Haller, Leverkusen-I. G. Werk, Germany,

assignor to General Aniline Works, Inc., New

York, N. Y., a corporation of Delaware No Drawing. Application November 26, 1937, Se-

rial No. 476,633. In Germany December 2,

8 Claims.

In this formula A stands for a triphendioxazine radical, B stands for the radical of an ice color w, coupling component, and n for one of the numtached to the m-positions with respect to the azine nitrogen atoms. I

My new dyestuffs are obtained by diazotizing triphendioxazines which contain in m-position to the azine nitrogen one or more amino groups and coupling with azo components, the compounds being selected in such a manner that the resulting dyestuffs are free from watersolubilizing groups.

Up to the present time diazotized triphehdioxazines which contain in the dyestuff molecule one or more amino groups have not been used for the manufacture of azodyestufis. In fact, not all amino-triphendioxazines can be transformed into their diazo compounds; for instance, in the case in which the amino groups stand in p-positionto the azine-nitrogen atoms, the nitrous acid has only an oxidizing effect and, with rearrangement of the quinoid linkages, there is obtained a compound which by reduction can be converted into the original amine. Probably this oxidation process proceeds as follows:

In contradistinction thereto diazotization can easily be effected if the amino group or groups in question stand in m-position to the azine-nitrogen. If thepositions in the triphendioxazine are numbered as follows:

the positions 2, 4, 6 and 8 are capable of bearin diazotizable amino groups. 7

bers 1 to 4, and the N=NB groups are at- The diazo and polydiazo compounds of these amines dissolve in water in form of their salts, with yellow to orange-red coloration. On coupling on the fiber with ice color coupling components they yield blue, brown and black shades of very good fastness properties.

The technical value of the new dyestuffs is to be primarily recognized in the excellent fastness to light of numerous combinations and'in their remarkable strength of color. As suitable ice color coupling components there may be mentioned by Way of example the arylides of ohydroxycarboxylic acids of the naphthalene series or other cyclic compounds, and the arylides of,

acetoacetic acid and the derivatives thereof.

It is surprising that when coupling tetrazotized diaminodioxazines, which moreover contain alkoxy groups in o-position to the diazotized amino groups, with acetoacetic arylides, which are typical yellow components, deep black shades are produced.

Triphendioxazines containing amino groups, used in the present invention as diazo components, can be obtained according to known processes (of. e. g., U. S. P. 2,092,387, 2,024,525 and 2,020,651). Besides the amino groups they may contain in the molecule other substituents as, for instance, halogen, alkyl, alkoxy, except watersolubilizing groups, such as the sulfonic acid and the carboxylic acid group.

The following examples illustrate the invention without being restricted thereto.

EXAMPLE 1 The yarn is The dyestuff corresponds to the following formula:

\OH l ('31 Ifil /OH @GONHO EXAMPLE 2 Cotton yarn is grounded in a solution which contains 1.5 g. of 2.3-hydroXynaphthoyl-;3-naphcos. of sulfonated castor oil and cos. of caustic soda lye of 39 B. with the addition of water, and the whole is made up with water to one liter.

Printing paste 15 g. of 2.6-diamin03.'7-dimeth0-xy-9.l0-dich10r0 triphenodioxazine are tetrazotized in 200 cos. of ice water with the addition of 50 ccs. of sulfuric acid and 5.5 g. of sodium nitrite.

are added 6.5 g. of crystallized sodium acetate and the orange colored solution is stirred into 500 g. of a wheat starch-tragacanth thickener.

After some time there 1 CH3 CH2 0 OQ O CH N=N O 0 CH3 CH3 I 1 l HI I I CH: 0 H3 C H: 0 OH:

thylamine per liter. After squeezing off, the ma- EXAMPLE 4 On substituting the 2.3-hydroxynaphthoyl-pnaphthylamine by 3 g. of diacetoacetyl-o-tolidine, there is obtained a bluish black.

EXAMPLE 3 Slop-padding solution 10 g. 01' diacetoacetic-o-tolidide are dissolved with The grounding of cotton yarn is effected in a solution which contains 3 g. of 2.3-hydroxynaphthoylxnaphthylamine per liter. For development there is used a solution (2.5 g. per liter, calculated on the base) prepared by diazoti- Zation of 2.7-diamino-Q.l0-dichloro-triphendioxazine of the formula:

0 01 N HzN- NHz After rinsing and soaping at the boil, there is obtained a navy blue.

On substituting the 2.7 -diamino-9.10-dichlorotriphendioxazine by the 2.6-diamino-dichlorotriphendioxazine, there is obtained a bluishblack.

EXAMPLE Cotton is impregnated with a solution which contains per liter 2 g. of 2-hydroxycarbazole-3- carboxylic acid-4-chloranilide. As developer there is used a tetrazo solution prepared from 2.8- diamino 9.10 dichlorotriphendioxazine in the 1. Water-insoluble azodyestuffs of the general formula:

wherein the Y radicals are identical and stand CH3 CH2 I CE:

for radicals selected from the group consisting of NELCO hydrogen, alkyl and alkoxy, B stands for the radical of an arylamide selected from the group consisting of arylamides of o-hydroxy-naphthoic acid, o-hydroxycarbazole carboxylic acid and acetoacetic acid, and n for one of the numbers 1 to 4, the N:NB groups being attached to the m-positions with respect to the azine-nitro- O 0 01 N I I N% 0/ 00 1 CH3 CH3 OH,

gen atoms and the B radicals being identical if n is greater than 1, yielding, when produced on the fiber, in general blue to black shades of good fastness to light.

2. Water-insoluble azodyestuffs of the formula:

wherein the B radicals are identical and stand for on (JOHN-Q01 radicals of an arylamide selected from the group consisting of arylamides of ohydroxy-naph thoic acid, o-hydroxy-carbazole carboxylic acid and acetoacetic acid, yielding, when produced on the fiber, brown to black shades of good fastness to light.

3. The water-insoluble azodyestufi of the probable formula:

yielding, when produced on the fiber, black shades of good fastness to light.

4. The water-insoluble azodyestuff of the formula:

/ 0 O.C2H5

yielding, when produced on the fiber, black shades of good fastness to light.

5. Fibers dyed with a dyestuff as claimed in claim 1.

6. Fibers dyed with a dyestufi' as claimed in claim 2.

7. Fibers dyed with a dyestuff as claimed in claim 3.

8. Fibers dyed with a dyestufi as claimed in claim 4.

J OSEF HALLER. 

